Insecticidal compositions and methods of killing insects using alpha,beta-dioxohydrocinnamonitriles

ABSTRACT

1. A METHOD FOR CONTROLLING INSECTS COMPRISING APPLYING TO SAID INSECTS AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA:   (R2-CO-C(-CN)=N-NH-),R,R1,R3-BENZENE   WHEREIN R IS HALO, ALKYL OF 1 TO 4 CARBONS, ALKOXY OF 1 TO 4 CARBONS, CYANO, TRIFLUOROMETHYL OR P-CHLOROPHENOXY, R1 IS HYDROGEN, HALO, TRIFLUOROMETHYL OR ALKYL OF 1 TO 4 CARBONS, R2 IS 2-THIENYL, AND R3 IS HYDROGEN OR HALO.

United States Patent US. Cl. 424-275 6 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to insecticidal methods and compositions employing a,fl-dioxohydrocinnamonitriles having the formula:

where R, R R and R are defined as follows: R is halo, loweralkyl (C -C loweralkoxy (C -C cyano, nitro, trifluoromethyl, phenylazo or p-chlorophenoxy; R is hydrogen, halo, trifluoromethyl or loweralkyl (C C R is hydrogen or halo; and R is phenyl, halophenyl, dihalophenyl, alkyl (C -C phenyl, loweralkoxy (C -41 phenyl, l-naphthyl, 2-furyl, or 2-thienyl.

This application is a divisional of our co-pending application, Ser. No. 250,338, filed on May 4, 1972, now US. Pat. 3,793,456, issued Feb. 19, 1974; which is a continuation-in-part of application Ser. No. 141,444, filed May 7, 1971, now abandoned.

The present invention relates to the use of certain hydrazones in insecticidal methods and compositions. It further relates to certain novel hydrazones used therein and to the preparation thereof.

More particularly, the invention relates to insecticidal methods and compositions employing hydrazones of 0a, dioxohydrocinnamonitriles having the formula:

ll C-Rg the novel hydrazones compounds thereof having unexpectedly high insecticidal activity, having the formula:

wherein Y is hydrogen, chloro or loweralkyl (C C n is 0, 1 or 2; and m is l or 2. Especially preferred com pounds therein are:

a,,8-dioxo-, a- (3-chloro-0-tolyl)hydrazone1hydrocinnamonitrile,

a,B-diOXO-, a- 3,4-dichlorophenyl) hydrazone1hydrocinnamonitrile,

u,[3-dioxo-, u- (2,4-dichlorophenyl hydrazone] hydrocinnamonitrile,

p-chloro-a,p-dioxo-, a- (p-chlorophenyl)hydrazone] hydrocinnamonitrile and tx,/3di0XO-, a- 2,4,5-trichl0r0phenyl )hydrazone] hydrocinnamonitrile.

Finally, it relates to the preparation of the above novel hydrazone compounds.

Illustrative hydrazones include:

hydrocinnamonitrile, a,]3-diOX0-, a- (2,5-dichlorophenyl)hydrazone] hydrocinnamonitrile, u,B-diOXO-, u-[ (p-chlorophenyl) hydrazone] hydrocinnamonitrile, a,}9-diOXO-, u-[ (p-phenylazophenyl) hydrazone] hydrocinnamonitrile, u,[3-dioxo-, a-[ (3,4-dichlorophenyl) hydrazone] hydrocinnamonitrile, u,/3di0X0-, a-[l-naphthylhydrazone];

hydrocinnamonitrile, a,}8-diOXO-, a-[ (m-chlorophenyl)hydrazone] hydrocinnamonitrile, a,B-diOXO-, ot-[(o-chlorophenyl) hydrazone] hydrocinnamonitrile, a,;9-diox0-, u-[4-chloro-0-t0lyl)hydrazone];

hydrocinnamonitrile, a,fi-diOXO-, a-[(2,5-dichlorophenyl) hydrazone] hydrocinnamonitrile, p-chloro-a,;8-dioxo-, a-[(p-chlorophenyl)hydrazone];

hydrocinnamonitrile, a,fi-dioxo-, oz- (p-tolylhydrazone);

2-furanpropionitrile, oz,B-diOXO-, oz-[ (p-chlorophenyl) hydrazone] 2-thiophenepropionitrile, a,p-dioxo-, a-[ (p-chlorophenyl)hydrazone] 1-naphthalenepropionitrile, m, 8-diox0-, a-[(p-ch1orophenyl hydrazone] acetanilide, 4'- (a-cyanophenacylidene)hydrazino]- N-methyl-;

butyronitrile, 2,3-dioxo-, 2- (p-chlorophenyl)hydrazone] hydrocinnamonitrile, a,B-diOXO-, u-[(3-ch1oro-2-methylphenyl) hydrazone] hydrocinnamonitrile, u,}3-dlOXO-, a-[(2,4,5-trichlorophenyl hydrazone] hydrocinnamonitrile, a, 3di0X0-, m-[(P-bromophenyl)hydrazone] hydrocinnamonitrile, u,fl-dlOXO-, a- (4-fluoro-3-methylphenyl) hydrazone] hydrocinnamonitrile, a,fi-dioxo-, a-[ (2,4,6-tribromomethyl)hydrazone] hydrocinnamonitrile, m-chloro-a,fl-dioxo-, a-[(2,5-dlchlorophenyl hydrazone] and the like.

The hydrazones are prepared by reacting an aniline of Formula II with a diazotizing agent in the presence of a mineral acid and further reacting the thus-formed diazonium salt with an aroylacetonitrile III. The synthetic method may be illustrated as follows:

(1) RrNOz BK NH2 R1 (2) RzCOCHzCN R II III ii Ra C-Rg NHN=C\ R1 CN wherein R is selected from the group consisting of an alkali metal, such as lithium, potassium or sodium and C -C loweralkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl and the like and HX represents a mineral acid, such as HCl, H 80 HNO and the like. R, R R and R are as above.

The relative quantities of the ingredients employed can be widely varied. For optimum yields, it is generally preferred to react equimolar quantities of the aniline and nitrite. Lower alcohols C -C water and mixtures thereof are among the preferred solvents for use in carrying out the synthesis. It is also preferred to employ a mineral acid in suflicient quantities to produce an acidic pH in the aqueous or alcoholic solvent and to adjust the reaction temperature to temperatures within the range of from about 10 C. to about +10 C. The preferred temperature is about C.

Sodium and potassium nitrite and methyl, ethyl or nbutyl nitrite are among the preferred diazotizing agents which are particularly well suited for use in the syntheses.

Preferred mineral acids include sulfuric, hydrochloric and hydrobromic acid. It is generally preferred to employ a slight excess of the acid over and above the stoichiometric amount required to form the substituted benzene diazonium salt.

After formation of the desired diazonium salt, the reaction mixture is preferably reacted further by adding it to a mixture of the appropriate aroylacetonitrile and a weak base, such as sodium or potassium acetate while the temperature is maintained at from about C. to about +10 C. The desired hydrazone of the a,B-dioxohydrocinnamonitn'le is produced thereby and may be recovered from the reaction mixture by any convenient means, such as, by filtration, centrifugation and the like.

It has been found that the hydrazones of Formula I and especially the novel hydrazones or,}3-dl0X0-, lX-[(3- chloro-o-tolyl)hydrazone] hydrocinnamonitrile and ,5- dioxo-, a. [(3,4 dichlorophenyl)hydrazone] hydrocinnamonitrile are useful as insecticides. They are particularly effective for controlling lepidoptera and mosquitoes, especially in the larval stages.

The insecticidal methods of the present invention involve contacting the insect to be controlled or the locus or area where insect control is desired with an insecticidally eifective amount of one or more of said hydrazones. Application of the active ingredient at a rate of from between about 0.5 and about 15 pounds per acre of the active ingredient is generally sufiicient to achieve the desired insect control.

For application of the hydrazones, it is generally preferred to employ them in combination with conventional pesticidal adjuvants and formulation aids. They may be advantageously employed with the use of either solid or liquid adjuvants and applied in the form of dusts, dust concentrates, wettable powders emulsifiable concentrates and the like.

Field application of these formulations may be made by conventional equipment, such as power dusters, boom and hand sprayers, spray dusters, addition to irrigation water, and the like.

The active ingredient may be initially formulated with a concentrated composition, comprising the active ingredient in a solid or liquid adjuvant which serves as a formulation aid or conditioning agent, permitting the concentrates to be further mixed with a suitable solid or liquid carrier.

Useful liquid adjuvants in which the toxicant is dissolved, suspended or distributed include, for example, xylene, benzene, lower alcohols C -C fuel oil or the like, with or without an emulsifying agent. For application, the resulting solution can be further diluted with either water or an organic diluent, such as deodorized kerosene. Concentrations in the range of from about 5% to about are generally suitable for initial solution. When diluted for application, suitable solutions may contain the active ingredient in concentrations of from about 0.5 p.p.m. to about 5000 p.p.m.

Suitable solid adjuvants include, for example, attapulgite, kaolin, talc or diatomaceous earth in granular or finely ground form. The active ingredient can be conveninently formulated with the solid adjuvants as dusts, dust concentrates, wettable powders, granulars and the like.

Dusts are generally prepared by grinding together from about 1% to 10% by weight of the hydrazone with a finely divided inert diluent such as attapulgite, kaolin, diatomaceous earth, talc, or fullers earth. These formulations can then be applied with dusting equipment to the foliage of agronomic crops or fields, meadows, forests or the like which are to be protected from insect attack or where insect control is desired. Application is generally sufficient to provide between about 0.5 and 15 pounds per acre of active material.

Dust concentrates are usually prepared in the same manner as dusts but generally from about 25% to 75% by weight of the active hydrazone and from 75 to 25% by weight of diluent are used.

Wettable powders are prepared in the same fashion as the dust concentrates, however, from about 1% to 5% by weight of an emulsifying agent and from about 1% to 5% by weight of a dispersing agent are usually included in such formulations, Polyethylene glycols, methoxy polyethylene glycols, sodium lignosulfonate, calcium dodecylbenzene sulfonate and the like are among the emulsifying agents and dispersing agents which can be used in these formulations. In practice, the wettable powders are generally dispersed in water and applied as a dilute spray to the vegetation or water where insect control is desired.

Usually, concentrations of the active ingredient of from about 10 p.p.m. to 1000 p.p.m. dispersed in the water of ponds, lakes, creeks, swamps and such will give excellent control of mosquito larvae. Excellent insect control and plant protection in fields, forests, crop lands and the like is generally achieved by application of the active ingredicut at rates of from about 1 to about 15 pounds per acre.

The invention is further illustrated by the following examples which are not to be taken as limitative thereof. In each case, the parts and percentages are by weight unless otherwise indicated.

EXAMPLE 1 Preparation of c p-Dioxohydrocinnamonitrile ot-(a,oz,a, u',a',ot-hexafiuoro-3 S-xylyl) hydrazone The 11,12,111,a',a',u-hexafluoro-3,S-xylidine 0.0250 mole) was added to 25 ml. of a stirred, ice-cold EXAMPLES 2-16 Preparation of Various a,fi-Dioxohydrocinnamonitrile Hydrazones A variety of a,;3-dioxohydr0cinnamonitrile hydrazones of Formula I were prepared by the general procedure of Example 1, employing the appropriately substituted aniline and cinnamonitrile, in lieu of the a,oc,oz,a',oz',o'-h6Xafiuoro-3,5-xylidine and p-oxohydrocinnamonitrile used therein, to produce the hydrozones set forth in Table I below. R which is in Table I, is in each case H.

TABLE I Calculated Found Example Percent; Melting number R R1 R2 yield point C.) C H N Cl C H N 01 Benzo Phenyl 43 145. 5-1480 76.24 4.38 14.04 76.53 4.44 14.11 m-Cl do 87.5 165-1655 63.50 3.55 14.81 12.50 63. 3.75 14.72 12.50 o-Ol H do. 92 126. 5-127.5 63.50 3. 55 14.81 12.50 63. 41 3.58 14.78 12.48 p-Ol O-CH! .do...- 89 156. 5-157 64.54 4.06 14.11 11.91 64. 75 4.15 14.17 11.97 2-01 5-01 do 88 127-127.5 56.62 2.85 13.20 22.29 55.68 3.40 12.22 20.73 p-Cl H p-Chlorophenyl.-. 226-228.1 56.62 2.85 13.20 22.29 56.51 2.90 13.18 22.41

........ (I) H Pheny1.- 250-251 67.48 5.03 17.49 67.30 4.97 17.52 CH3bN- 9 p-Cl H 2-fury1 83 172. 51-1713 57.05 2.95 15.36 12.95 57. 06 2. 96 15. 39 13.09 p-Cl H 2-thienyl 86 220-2205 53.89 2.78 14.50 12.24 55.41 2. 96 14.89 12.46 p-Gl H l-naphthyl 54 174-175 68.37 3.63 12.59 10. 62 69.14 3 12.48 10.69 3-N0g (*rCH Phen p-Ol H 88 175-1755 63.48 3.56 63. 41 3 67 14.89 13.08 'OCHS o-No 96 182-183 59. 26 3. 73 17. 28 3. 83 17.54 Phenylazo H 83 179-180 71.37 4.28 19.82 71.03 4.06 19.66 2-0 CH1 5-01 84 191-193 61. 25 3. 85 13. 39 11. 30 61. 16 3. 72 12. 94 11. 26

1 Decomposes.

6N- sulfuric acid Solution. The hydrosulfate salt precip- EXAMPLE 17 itated as a flocculent white solid. This mixture was stirred and maintained in an ice bath while a solution of the sodium nitrite (1.72 g., 0.0250 mole) in a little water was added dropwise. The yellow diazom'um salt solution was then filtered to remove a small amount of precipitate. The fi-oxohydrocinnamonitrile (3.62 g., 0.0250 mole) was slurried in 25 ml. of 2B ethanol, and a solution of sodium acetate (12.30 g., 0.150 mole) in 40 ml. of water was added. This mixture was stirred and maintained in an ice bath while the diazonium salt solution was added dropwise. Thereafter, the solution was stirred with cooling for an additional hour and the desired product produced Preparation of a,fi-Dioxo-a-[(p-chloropheny1)hydrazone] -hydro cinnamonitrile stroyed by addition of sulfamic acid, and the resulting solution was filtered. The filtrate was added dropwise over a period of 15 minutes to a mixture of benzoylacetonitrile (2.9 g., 0.02 mole) in 30 ml. of methanol, 10 ml. of water, and 15 g. of solid sodium acetate at C. The resulting mixture was stirred overnight. The desired product was isolated by filtration, washed with water, and dried in vacuo at 80 C., yielding 5.0 g. (88%).

Purification was effected by successive recrystallizations from aqueous ethanol to give a product having an m.p. of 175 C.175.5 C.

EXAMPLE 18 Cl CH3 Cl OH;

N=N C1 Q-C O-CEN-NH- 5.66 Grams (0.04 mm.) of 3-chloro-0-toluidine was dissolved in 60 ml. of 3N HCl (0.186 m.), and the solution was cooled to 0 C. 3.6 Grams (0.04 m.) of potassium nitrite, which was dissolved in 10 ml. of water, was then added dropwise, maintaining the temperature at 0 C. The diazonium salt solution was then added to a solution of 5.81 grams (0.04 m.) of benzoyl acetonitrile and 30 grams (0.365 m.) of sodium acetate dissolved in 300 ml. of water and 200 ml. of methanol, over approximately 5 minutes with rapid stirring at room temperature. The mixture was stirred for one hour at room temperature, and the bright yellow solids were collected by filtration. The crude product was recrystallized from 300 ml. of ethanol to 50 ml. of methyl ethyl ketone, water was added at reflux until the cloud point was reached (approximately 50 ml. necessary). 9.45 Grams (80% theory) of yellow needles were obtained. Melting point is 133 C. to 133.5 C.

Analysis.Calculated for N OC1C H C, 64.56; H, 4.03; N, 14.12. Found: C, 64.16; H, 4.00; N, 14.08.

As in the case of the preparation of oz, fl-dioxo-, oz- [(3 chloro-0-tolyl)hydrazone] hydrocinnamonitrile, the other novel hydrocinnamonitrile insecticides mentioned above, e.g., a,}3-dl0XO-, u-[(3,4-dichlorophenyl) hydrazone hydrocinnamonitrile, can also be prepared by reacting the appropriately substituted aniline at a temperature of from about l0 C. to about +10 C. with a compound of the formula R NO in a solvent rendered acidic by the addition of a mineral acid to form a diazonium salt solution of said aniline, and reacting the diazonium salt in solution to form said hydrazone by adding said diazonium salt to a mixture of a weak base and aroylacetonitrile,

wherein R is a member selected from the group consisting of alkali metals and C -C loweralkyl groups.

8 EXAMPLE 19 Preparation of Various a,}3-Dioxohydrocinnamonitrile Hydrazones A variety of a,fl-dioxohydrocinnamonitrile hydrazones of Formula I were prepared by the general procedure of Example 1, employing the appropriately substituted aniline cinnamonitrile. The compounds produced are set forth in Table II below.

EXAMPLES 20-33 The insecticidal activity of the compounds of Formula I is demonstrated by the following tests using the test procedures set forth below.

Southern Armyworm (Pradenia eridania Cram.)

Compounds to be tested are made up as 0.1% solutions in 65/35 acetone-water mixtures. Sieva lima bean leaves are then dipped in the selected test solution and set in a hood to dry. When dry, they are placed in petri dishes lined on the bottom with a moist filter paper and ten third-instar armyworms are added to each dish. The dishes are covered, held at F., 60% relative humidity for two days and then examined and mortality counts made. Untreated leaves are used as controls.

Tobacco Budworm (H eliothis vireseus) Compounds to be tested are made up as 0.1% solutions in 65/35 acetone-water mixtures. Small leaves from cotton plants are then dipped in the selected test solutions and air dried. After drying, they are placed in a small medicine cup with a dental wick saturated with water and one third-instar tobacco budworm and held in a constant temperature and humidity room for three days. At the end of the holding period all cups are examined and mortality counts made. At least ten replicates per test solution are used.

The data obtained are in each case set forth in Table III below. R which is unshown in Table III, is in each case H.

TABLE III Percent control Southern Tobacco armybudworm, worm, Ex. concentraconcentra- No. R R1 R2 tion 0.1% tion 0.1%

100 90 as 100 100 so 10 90 60 95 so 50 60 100 100 100 60 100 so 100 90 BL... 3-CF3 100 100 a2 2-01 100 100 33 p-Phenylazo- 100 100 EXAMPLES 34-42 The larvicidal activity of the compounds of Formula I is demonstrated in the following tests using mosquito larvae. The test procedure is as follows:

Mosquito Larvae (Anopheles quadrz'maculatus Say) Groups of 25 larvae of the common malaria mosquito are transferred with a medicine dropper to a ml. beaker containing 25 ml. of water. The test compound is formulated as an emulsion containing 0.1 gram of test material, 0.2 gram of Alrodyne 315 emulsifier, a nonionic polymeric emulsifier by Alrose Chemical Company, 10 ml. of acetone and 90 m1. of water. This 1000 ppm. emulsion is diluted ten-fold with acetone-35% water to give 100 ppm. One milliliter of the 100 p.p.m. emulsion is pipetted into 225 ml. of water in a 400 ml. beaker and stirred vigorously. The larvae in 25 ml. of water are added, giving a concentration of 0.4 ppm. Mortality counts are made after 24 hours at F. Data obtained are provided below in Table IV. R which is unshown in Table IV is in each case H.

EXAMPLE 43 Foliar Residual Activity of Phenylhydrazones The foliar residual activity of the phenylhydrazones and commercial standards is shown in Tables V, VI, VII and VIII. The rates in all the tables are expressed in pounds of actual ingredient per acre. All materials formulated as wettable powders (WP) and emulsifiable concentrates (EC) were applied in 86 gallons of water per acre. Application was made by a single fiat-top nozzle moving on an overhead track. Materials formulated in 64.5% acetone, 35% water, and 0.5% Alrodyne 315, a polyethylene glycol fatty ester non-ionic surfactant by Geigy Chemical Corporation were applied in the formulation vehicle at an equivalent of 86 gallons per acre. Following application, the treated plants are placed on greenhouse benches and permitted to dry. At various time intervals thereafter, treated leaves are removed from the plants, placed in petri dishes with moist filter papers on the bottoms thereof and containing 5 or 10 southern armyworms or gypsy moth larvae. Mortality counts are made after three days of exposure.

TABLE IV Example number For bioassays with tobacco budworms, the excised leaves are cut into five sections, and each section is placed in a. one-ounce plastic medicine cup containing a one-inch dental wick saturated with water, and one-third Instar tobacco budworm. Mortality counts are made after three days of exposure.

TABLE V Foliar residual activity of phenylhydrazones on lima bean plants bioassayed with Southern armyworms Percent mortality after age of Rate, residue on plants ofpounds Formulation Structure per acre 0 weeks 2 weeks 3 weeks 4 weeks 50% WP Pfi 100 100 100 93 C O-(|3=NNH Cl 1 100 100 100 100 50% WP Cl 100 98 100 1 100 100 100 100 01 0% WP. ..2 3/2' 100 100 90 01-- C O(|3=NNH Cl 1 100 100 100 50% WP cheek A e 1 0 o 0 50% WP 50 30 C O-(|J=N-NII C1 1 80 50 20 50 WP Cl 80 40 50 WP. y,; 80 50 50 60 c1- c O--Cl2=NNH-Cl 1 100 so 50 50 50% WP check 20 40 0 50 TABLE VI Foliar residual activity of phenylhydrazones on lima bean plants bioassayed with southern armyworms Percent mortality after age of residue e, on plants ofpounds Formulation Structure per acre Week 1 week 2 weeks 3 weeks 64.5? A 857 W 0.57 Alrodyne 315 3, 5 100 78 93 73 CO('J=NNH 1 100 5a CHa C1 D0 H 100 90 78 25 -C O-C=NNH Cl 1 100 100 100 65 D0.-. Cl M 100 18 l 1 100 100 78 100 D0..-..'.-..' 100 100 100 95 CO(|' =N-NH 100 100 100 100 50% WP n 100 100 100 95 cic OC=N-NHC1 1 100 100 100 95 50% WP cheeko o o o Foliar residual activity of phenylhydrazones on cotton plants bioassayed with tobacco budworms 64.5 A,35 W 0.5 Airod me 315..... y 90 50 0 y CO(|J=NNH 1 100 100 40 CH: C1

D0 $6 100 100 40 C O(IJ=N-NH Ci 1 100 100 100 60 D0 Cl $6 80 1 90 G N 01 C1 D0 $4 20 C O-(IJ=NNH Cl 1 90 7O 90 20 Cl OO-(IJ=NNH 50%WPcheck 0 20 10 0 N0rE.-A=Acetone; W=Water.

TABLE VII Follar residual activity of experimental insecticides and standard on lima bean, radish, and tobacco plants aged in the greenhouse and bioassaycd with Southern armyworms Percent mortality of Southern armywonns after 3 days of exposure R t Age of residue on plants in weeks ee pounds Lima bean plants Radish plants Tobacco plants Formula- Structure per tion acre012340123401234 0 I3= NH 100 100 L 100 88 80 100 100 100 100 100 CH3 Cl 50%WP 01 J15 100 63 68 33;: 100 90 100 80 85 100 100 100 73 93 I 1 100 98 100 60 73 100 100 95 100 50%WP. M 100 100 85 65 90 100 100 100 100 95 100 100 100 98 85 (I;=N-NH Cl 1 100 100 98 83 60 100 100 100 100 100 TABLE VII-Continued Percent mortality of Southern armywo rms after 3 days of exposure R t Age of residue on plants in weeks a e pounds Lima bean plants Radish plants Tobacco plants Formulaper tion Structure acre 1 2 3 4* 0' 1 2 3 4* 0 1 2 3 4* 50%WP- 100 88 78 63 90 100 100 100 100 95 100 100 100 98 93 -C0(|3=NNH- Cl 1 100 100 100 95 90 100 100 100 100 100 Cl- C 0-g =N-NH C1 1 100 100 100 95 95 100 100 100 100 100 Southern armyworms small-had to use second instar instead of third.

TABLE VIII Foliar residual activity of experimental insecticides and standards on cotton plants aged in the greenhouse and bioassayed with various insects Percent mortality after 3 days of exposure Age of residue on plants in weeks Rate, Tobacco budworm Southern armyworm Gypsy moth larvae Formulapounds tlon Structure per acre 0 1 2 3 4 0 1 2 3 4* 0 1 2 3 50% WP 36 75 13 78 22 80 95 85 80 100 COC=NNH 1 88 63 78 33 100 100 100 95 100 89 100 100 90 JI N 50% WP 01 L6 13 56 75 8O 75 25 PH" 3 so 62 56 c1 1 100 100 89 1 ymo so 89 11 100 100 100 100 100 50%, Cl-OOE=NNHCI 1 100 75 100 44 70 100 100 100 100 100 Southern armyworms small-used second instar, not third.

EXAMPLE 44 fiat-tip spray nozzles at a pressure of 25 p.s.i. and at a tractor speed of 4 miles per hour. The foliage of sixty-foot Fleld Evaluatlon of Test Compounds rows of potatoes were treated on schedule for control of Test materials were applied at the rate Of One pound 60 Colorado Potato Beetle (Leptinotarsa aecemlineata). The

actual ingredient in 57 gallons of water per acre. Applicadata obtained for the test compound and untreated contion was made by a C0 power-pack sprayer with three trol are set forth in Table IX below.

TABLE IX Control 77 2 1 EXAMPLE 4s The effectiveness of the phenylhydrazone in the control of Imported Cabbage Worm (Pieris rapae) on thirty-one foot rows of cabbage was determined using the application procedure of Example 44. The results obtained are set forth in Table X below.

16 EXAMPLE 47 Procedure for small scale field trials for compounds of the present invention on corn is as follows. The experimental materials were applied at the rate of 1 lb. actual 5 ingredient in 65 gallons of water per acre. Application was made by a portable compression sprayer at the speed TABLE X No. of worms per head of Treatment Structure Formulation cabbage schedule 0 EN 507 WP 1.0 4 applications,

| a 7-day schedule.

0 OC=NNH Cl Control 4. 7

EXAMPLE 46 Effectiveness of test compounds against insects of the order Coleoptera is shown in the following test.

The test procedure employed to determine the efficacy of compounds of the present invention for controlling insects of the order Coleoptera is the same as that described above for the Southern Armyworm which are of the order Lepidoptera, excepting that cucumber beetles and Mexiof normal walking. Six feet by fourteen feet plots replicated three times were treated three times on a weekly schedule. Ten corn plants per plot were examined for fall armyworms (Spodoptera frugiperda). The results obtained are set forth in Table XII below.

TAB LE XII Use of phenylhydrazones in foliar treatment in field control of the Fall armyworm (Spodopterafruqtperdn) on corn Rate, pounds Total actual worms Formuingredient in three Structure lation per acre replicates 0 N WP 1 76 Q-o o-i:=N-NH--o1 CI 50% W]? 1 19 0 N Q s C N 50% WP 1 26 o1- 0 O-l=N-NH-C1 88 Control can bean beetles are substiuted for Southern Armyworms.

Data obtained are reported in Table XI below.

TABLE XI Use oi several phenylhydrazones against adult spotted cucumber beetle (Diabiotica undecimpunctata howurdt) and adult Mexican bean beetle (Epilachna varivestis) Adult spotted Adult Concentracucumber Mexican Structure tion in p.p.m. beetles 1 been beetle i Cl 1, 000 t Q0 OC=NNH 01 Cl 1, 000 80 50 F C OC=N-N H 01 CH; Cl 1, 000 80 50 r Q4: 0C=NNH-- 2-day mfii'tality data. 1 4-day mortality data.

17 We claim: 1. A method for controlling insects comprising applying to said insects an inseeticidally efiective amount of a compound of the formula:

wherein R is halo, alkyl of l to 4 carbons, alkoxy of l to 4 carbons, cyano, nitro, trifluoromethyl or p-chlorophenoxy; R is hydrogen, halo, trifluoromethyl or alkyl of 1 to 4 carbons; R is Z-thienyl; and R is hydrogen or halo.

2. The method of Claim 1, wherein the insects are on the foliage of agronomic crops.

3. The method of Claim 1, wherein the insects are mosquito larva.

4. The method of Claim 3, wherein the mosquito larva are in water.

5. The method according to Claim 1, wherein the compound has the formula:

18 wherein R is halo, alkyl of 1 to 4 carbons, alkoxy of 1 to 4 carbons, cyano, nitro, trifluoromethyl or p-chlorophenoxy.

6. An insecticidal composition comprising a suitable solid carrier in admixture with an insecticidally effective amount of a compound of Claim 1.

References Cited UNITED STATES PATENTS 3,150,151 9/1964 Urbschat et al. 260-493 3,157,569 11/1964 AddOr et a1 26O465 OTHER REFERENCES Dubenkoet al.: zh. Org. Khim, Vol. 5, No. 3, pp. 517- 20, 3/ 1969.

JEROME D. GOLDBERG, Primary Examiner A. J. ROBINSON, Assistant Examiner US. Cl. X.R. 260-332.3 C 

1. A METHOD FOR CONTROLLING INSECTS COMPRISING APPLYING TO SAID INSECTS AN INSECTICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA: 